A substance for reversibly absorbing and desorbing hydrogen is disclosed. The substance comprises a complex dispersing 0.8-20% by weight of one or more than two oxides selected from la, Ce, Nd, Pr, Sm and Eu into Zr(FeV)x (0.01≦x≦0.88).
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1. A substance for reversibly absorbing and desorbing hydrogen, comprising a complex dispersing 0.8-20% by weight of one or more than two oxides selected from la, Ce, Nd, Pr, Sm and Eu into Zr(FeV)x (0.01≦x≦0.88).
2. A substance for reversibly absorbing and desorbing hydrogen as claimed in
3. A substance for reversibly absorbing and desorbing hydrogen as claimed in
4. A substance for reversibly absorbing and desorbing hydrogen as claimed in
5. A substance for reversibly absorbing and desorbing hydrogen as claimed in
6. A substance for reversibly absorbing abd desorbing hydrogen as claimed in
7. A substance for reversibly absorbing and desorbing hydrogen as claimed in
8. A substance for reversibly absorbing and desorbing hydrogen as claimed in
9. A substance for reversibly absorbing and desorbing hydrogen as claimed in
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Field of the Invention
The present invention relates to a substance for reversibly absorbing and desorbing hydrogen, and its isotope, particularly a reversible hydrogen and its isotope absorbing-desorbing substance which is easy in hydrogenation and large in hydrogen absorbing and desorbing rate, more particularly, to a reversible hydrogen and it's isotope absorbing-desorbing substance with a comparatively high hydride composition and showing a lower equilibrium pressure than an atmospheric pressure at a temperature of less than 300°C, and also for getting the other gasses.
Hitherto, as a substance showing a lower hydrogen dissociation pressure than an atmospheric pressure at a temperature of less than 300°C among hydrogen getting materials, Ti, Zr, Hf and the like have been known. However, these metals are covered with strong oxides and nitrides, so that in order to obtain a hydrogen-gettable clean active surface, there is required a pretreatment for once sublimation by a sputtering method or heat-treatment at a high temperature of 700°-1,000°C
Recently, there has been tried improvement of a pretreatment such as activation by adding 2nd, 3rd, 4th, . . . elements to these metals to form an alloy, and controlling the hydrogen dissociation pressure characteristic by adding the 2nd, 3rd and 4th elements, or enlarging a reversible absorbing-desorbing rate of hydrogen.
However, among these metals, Zr-Al, Zr-Ni alloys, for instance, should be treated with heat-treatment or activation at a high temperature such as 450°-750°C, and even if Zr-V alloy can reversibly absorb and desorb hydrogen without an initial activation treatment, if the alloy is exposed to hydrogen gas of about 0.5 kg/cm2 when a temperature of initially absorbing hydrogen is ZrV0.15, a temperature is high such as about 230°C and an absorbing rate at that time is slow. Further, in Zr-V alloy, although no powder treatment is required, there is a viscosity to some extent and comparative solid, so that it is difficult to adjust this alloy to a desired size, that is, cutting and crushing.
Further, there has also been known intermetallic compound Zr-V-O and the like stabilized by oxygen, but there are such disadvantages that an activation treatment is required and regulation of a sample grain size is difficult because of hard alloy. There have been known to control a hydrogen dissociation pressure, to regulate a sample grain size and to improve characteristics to gas other than hydrogen gas by adding the 4th and 5th elements to an alloy stabilized with oxygen and forming an intermetallic compound such as Zr-Ti-V-Fe-O, but with the increase of kinds of addition elements, it has been difficult to regulate the substance to a desired composition.
The present inventors have studied and examined reversible hydrogen absorbing-desorbing materials showing a lower hydrogen equilibrium pressure than an atmospheric pressure with a comparatively high hydride composition at a temperature of less than 300°C and the material having a low temperature when initially absorbing hydrogen and a sufficiently quick rate of absorbing and desorbing hydrogen by excluding various problems inherent to these prior materials. As a result, the inventors have found that the object can be achieved by dispersing a specified amount of a certain kind of rare earth oxide into Zr(FeV) having a specified composition to form a complex.
Fe-V is less expensive than V, and the complex is substantially equal to that obtained by dispersing a specified amount of a kind of rare earth oxide into Zr-V.
Therefore, an object of the invention is to provide at a low cost a reversible hydrogen absorbing-desorbing substance showing a lower hydrogen equilibrium pressure than an atmospheric pressure at a temperature of less than 300°C in a comparatively high hydrogenation composition having a large hydrogenation reaction rate without requiring any initial activation treatment.
According to the invention, there is provided a substance for reversibly absorbing and desorbing hydrogen comprising a complex dispersed 0.8-20% by weight of an oxide of more than one element selected from La, Ce, Nd, Pr, Sm, Eu into Zr(FeV)x (0.01≦x≦0.88).
In this invention, zirconium-iron-vanadium as a matrix should be Zr(FeV)0.01-0.88 in composition.
The substance of this invention increases the activity to hydrogen gas as the (FeV) composition is increased as well as the mother alloy, and has a property of varying temperature characteristic, hydrogen equilibrium pressure, and composition characteristic. When this composition is smaller than the above range, the effect of increasing the activity to hydrogen gas is not so conspicuous, so that a desired object cannot be attained, and when the composition exceeds the above range, it is not preferable because activity to hydrogen does not increase.
The oxides of the elements dispersed in the matrix are one or more than two oxides selected from La, Ce, Nd, Pr, Sm, Eu, and the amount thereof is 0.8-20% by weight.
The substance of this invention has such property that the activity to hydrogen gas is increased as the addition amount of the rare earth oxide increases and the temperature-hydrogen equilibrium pressure characteristic is scarcely changed, but when the addition amount does not satisfy the above range, the effect of increasing the activity is not remarkable, and when the amount exceeds the above range, there is no more effect to the activity and the hydrogen absorption amount is only reduced, so that neither case is preferable.
It is preferable in view of the stability of efficiency that the oxides of these elements are in the most stable oxidation condition, that is, La2 O3, CeO2, Ce2 O3, Nd2 O3, Pr6 O11, Sm2 O3, En2 O3, but there is no particular limitation. Oxides of lower valence or non-stoichiometric oxidation condition or their mixed condition are also preferable.
As means for manufacturing the substance of the invention, various methods are employed, and the most preferable method is to regulate high pure zirconium and high pure iron-vanadium and a mixture of one or more than two rare earth oxides mentioned above (inclusive of Misch metal oxide) to form respective predetermined compositions and to act dissolve them in an inert air current such as argon and the like.
Alternatively, there are such methods that rare earth oxides are not directly mixed but rare earth pure metal is mixed and melted in an oxidizing atmosphere, and that a small amount of oxide such as Fe-V or Zr is mixed and melted.
Further, the substance according to the invention can extremely easily get impure gas such as oxygen, nitrogen, carbon monoxide, carbon dioxide, methane, steam and the like other than hydrogen gas. In addition, the substance according to the invention can be easily ground as compared with Zr(FeV) as a matrix, and not too brittle in general, and has excessive viscosity.
From these results, the substance according to the invention does not require any activation treatment in case of the initial hydrogen even in any composition, and a hydrogenation rate at that time is large and a reversible absorbing-desorbing rate is advantageously large.
Further, the reversible hydrogen absorbing-desorbing substance of this invention has various advantages such that grinding is easy, the temperature condition and the like in case of the initial hydrogenation is mitigated without almost changing the temperature-pressure-composition characteristic of the mother alloy different from the alloy improvement by the conventional 3rd element addition, and the reaction rate is quickened, and further other impure gas is got.
With these advantages, the reversible hydrogen absorbing-desorbing substance of this invention can be used for refining and separation of hydrogen gas, hydrogen gas pressure control of vacuum machines and the like, hydrogen gas getter including isotope, non-volatile getter, any actuator utilizing its high absorbing-desorbing rate at near atmospheric pressure and the like.
FIGS. 1 and 2 are characteristic diagrams showing initial activity of the substance for reversibly absorbing and desorbing hydrogen according to the present invention, and
FIG. 3 is a diagram showing equilibrium hydrogen pressure to temperature characteristics of the substance for reversibly absorbing and desorbing hydrogen according to the present invention in case of changing hydrogen composition of the hydride.
The invention will be explained by referring to examples hereinafter.
These examples are described with preferable specified compositions and other conditions, but these examples are an illustration only and the invention is not limited to these examples.
In order to form compositions shown in Table 1, respectively, there were used Zr metal powder (purity: more than 99.7%), Fe-V metal piece (purity: more than 99.7%), CeO2 (purity: more than 99.0%), Nd2 O3 (purity: more than 99.0%), Pr6 O11 (purity: more than 99.0%), Sm2 O3 (purity: more than 99.0%), Eu2 O3 (purity: more than 99.0%) and mixed rare earth oxide (consisting of 30 wt % of La2 O3, 50 wt % of CeO2, 15 wt % of Nd2 O3, 4 wt % of Pr6 O11 and 1 wt % of Sm2 O3), respectively, arc melted in an argon air current and regulated into a reversible hydrogen absorbing-desorbing material.
The thus obtained material was ground into 20-40 meshes, weighted by 4 g, charged in a hydrogen absorbing-desorbing reactor, vacuum exhausted to 10-2 Torr in the reactor, introduced hydrogen having 99.9999% purity into the reactor with a pressure of about 0.6 kg/cm2, the material temperature was maintained at 30°C for 10 minutes, then the temperature was raised from 30°C to 300°C at a rate of 5°C/min, and by measuring the sample temperature and the pressure in the reactor, the temperature that the sample was started to absorb hydrogen and the initial hydrogen absorbing rate were examined. Thus, the indices of the hydrogen absorption starting temperature and the absorbing rate at the time of the initial hydrogen absorption are as shown in Table 1. Further, the saturated hydrogen absorbing amount at the temperature of starting absorption of initial hydrogen in each sample (converted into STP) is as shown in Table 1.
FIG. 1 is a graph showing the time change of a hydrogen pressure in a reactor when materials of Example No. 22 (solid line (I)), Example No. 14 (solid line (II)) and Zr(FeV)0.19 (solid line (III)) as mother alloy thereof and ground to 20-40 meshes, charged in the above reactor, after vacuum exhausted to 10-4 Torr in the reactor, a hydrogen pressure of 0.6 kg/cm2 is given, 30°C is maintained for 10 minutes, and the temperature is raised to 300°C at a rate of 5°C/min.
In FIG. 1, the abscissa shows time, the ordinate shows a pressure in a reactor at that time by a solid line and a temperature in the vicinity of a sample at that time by a one-dot line.
FIG. 2 is a graph showing the time change of a hydrogen pressure when testing materials of Example No. 30 (solid line A), Example No. 27 (solid line B), Example No. 22 (solid line C), Example No. 5 (solid line D) and respective mother alloys Zr(FeV)0.88 (broken line a) and Zr(FeV)0.55 (broken line b), Zr(FeV)0.19 (broken line c) and Zr(FeV)0.05 (broken line d) under the same condition as in the case shown in FIG. 1.
In FIG. 2, the abscissa shows time, the ordinate shows a pressure in a reactor at that time by a solid-broken line, and a sample temperature by one-dot line.
FIG. 3 is a graph showing the hydrogen pressure temperature characteristic of a sample measured by grinding a material of Example No. 22 into 20-40 meshes, weighted by 4 g in a vacuum measuring hydrogen absorbing-desorbing container, continuously heating and vacuum exhausting the whole container at 250°C for 48 hours with the use of a cryopump, thereafter sealing a sample system from the exhaust system, introducing predetermined hydrogen gas at a room temperature and absorbing to the sample, then raising a temperature from the room temperature to about 350°C by balancing the hydrogen pressure, and returning to the room temperature in the same manner.
In FIG. 3, the abscissa shows a hydrogen pressure in the container charged said sample therein, that is, shows an equilibrium hydrogen pressure of said sample at that temperature, and the ordinate shows a sample temperature at that time (shown by (1000/T (1/k)) and (°C.)).
In FIG. 3, the solid line shows the time of absorbing hydrogen and the broken line shows the time of dissociating hydrogen, wherein (1) shows that the hydrogen content in said hydride is 2.5% of the saturated hydrogen absorbing amount, (2) shows 5%, (3) shows 10%, and (4) shows 15%, respectively. In each example, hydrogen is extremely quickly absorbed and desorbed to reach equilibrium, and shows the hydrogen pressure-temperature characteristic as shown in FIG. 3.
Further, in case of this pressure measurement, the pressure range from 10-5 to 10-2 Pa carries partial pressure measurement of hydrogen gas, and the pressure range higher than 10-2 Pa carries total pressure measurement with the use of an ionizer vacuum meter.
The material of Example No. 22 was ground into 20-40 meshes, weighed by 4 g and contained in a stainless vacuum measurement hydrogen absorbing-desorbing container (A) and the sample was not contained in said container (B). Both (A) and (B) were continuously heated and vacuumed at 150°C for 24 hours with the use of a cryopump and back to a room temperature, sealed from the exhaust system, and examined the time change of respective CO--N2 partial pressures within said containers (A) and (B), and as a result, at a room temperature of 20°C, the container (A) shows the increase of CO--N2 component at a ratio of 2.19×10-14 Torr l/sec, and the container (B) shows the increase of CO--N2 at a ratio 3.51×10-10 Torr l/sec. Therefore, even at a room temperature of 20°C, said sample absorbs the CO--N2 content at an absorbing rate of 3.51×10-10 Torr l/sec. Further, temperatures of both the containers (A) and (B) raised from 25°C to 250°C at a rate of 15°C/min, and the time change of the CO--N2 partial pressure were examined in the same manner as described above, and as a result, the container (A) shows 1.50×10-5 Pa at a room temperature and a partial pressure of 6.50×10-6 Pa at 250°C, and the container (B) shows 2.30×10-4 Pa at a room temperature and 2.30×10-3 Pa at 250°C Therefore, it means that said sample absorbs the CO--N2 component of 1.75×10-9 Torr l/sec during this period. Further, the temperature when the CO--N2 partial pressure was reduced in the container (A) was about 40°C
The material of Example No. 22 was ground into 20-40 meshes, weighed by 4 g and contained in a stainless vacuum measurement hydrogen absorbing-desorbing container (A) and the sample was not contained in said container (B). Both (A) and (B) were continuously heated and vacuumed at 150°C for 24 hours with the use of a cryopump and back to a room temperature, sealed from the exhaust system, and examined the time change of respective CO2 partial pressures within said containers (A) and (B), and as a result, at a room temperature of 20°C, the container (A) shows the increase of CO2 component at a ratio of 2.89×10-15 Torr l/sec, and the container (B) shows the increase of CO2 at a ratio 2.34×10-12 Torr l/sec. Therefore, even at a room temperature of 20°C, said sample absorbs the CO2 content at an absorbing rate of 2.34×10-12 Torr l/sec. Further, temperatures of both the containers (A) and (B) raised from 25°C to 250°C at a rate of 15°C/min, and the time change of the CO2 partial pressure was examined in the same manner as described above, and as a result, the container (A) shows 8.10×10-7 Pa at a room temperature and a partial pressure of 1.60×10-6 Pa at 250°C, and the container (B) shows 1.00×10-6 Pa at a room temperature and 2.40×10-5 Pa at 250°C Therefore, it means that said sample absorbs the CO2 component of 1.83×10-11 Torr l/sec during this period.
Zr(FeV)0.19 Nd2 O3 10 wt % and Zr(FeV)0.19 Pr6 O11 10 wt % are not shown in Table 1 as examples, but can be expected that it is possible to obtain the same effect as that examples shown in Table 1.
Moreover, the following materials are also not shown in Table 1, but can be expected that it is possible to obtain the same effect as that of examples shown in Table 1.
Zr(FeV)0.19 La2 O3 p wt %, CeO2 q wt %
Zr(FeV)0.19 La2 O3 p wt %, Nd2 O3 q wt %
Zr(FeV)0.19 La2 O3 p wt %, Pr6 O11 q wt %
Zr(FeV)0.19 CeO2 p wt %, Sm2 O3 q wt %
Zr(FeV)0.19 CeO2 p wt %, Eu2 O3 q wt %
Zr(FeV)0.19 Nd2 O3 p wt %, Pr6 O11 q wt %
Zr(FeV)0.19 Sm2 O3 p wt %, Eu2 O3 q wt %
(In the above materials, 0.8≦p+q≦20)
Zr(FeV)0.19 La2 O3 p wt %, CeO2 q wt % Sm2 O3 r wt %
(In this material, 0.8≦p+q+r≦20)
Zr(FeV)0.19 La2 O3 p wt %, CeO2 q wt % Sm2 O3 r wt %, Eu2 O3 s wt %
(In this material, 0.8≦p+q+r+s≦20)
Zr(FeV)0.19 La2 O3 p wt %, CeO2 q wt % Nd2 O3 r wt %, Sm2 O3 s wt % Eu2 O3 t wt %
(In this material, 0.8≦p+q+r+s+t≦20)
Furthermore, the following substances show such excellent properties as those of the present invention. The substance is that comprising a complex dispersed 0.8-10% by weight of an oxide of more than one element selected from La, Ce, Nd, Pr, Sm and Eu into the material (Zr1-x Lx)(FeV)y, (Zr(FeV)1-z Mz)y or (Zr1-x Lx)((FeV)1-Z Mz)y (In the materials, L is one or two elements selected from Ti and Hf, M is one or more than two elements selected from Cr, Mn, Fe, Co, Ni, Cu and Al and further
0.05≦x≦0.95
0.01≦y≦0.88
0.05≦z≦0.5)
The invention is not limited to the above mentioned embodiments.
| TABLE 1 |
| __________________________________________________________________________ |
| hydrogen indices of |
| absorbing absorbing rate at |
| example |
| material(substance) |
| amount |
| temperature |
| the time of |
| number |
| composition (cc/g) |
| (°C.) |
| absorption |
| __________________________________________________________________________ |
| 1 Zr(FeV)0.05 La2 O3 |
| 1% by |
| 213 250 less than 0.5 kg/cm2 |
| weight within 180 min. |
| 2 Zr(FeV)0.05 CeO2 |
| 1% by |
| 210 250 less than 0.5 kg/cm2 |
| weight within 180 min. |
| 3 Zr(FeV)0.05 mixed rare |
| 1% by |
| 215 250 less than 0.5 kg/cm2 |
| earth oxide weight within 180 min. |
| 4 Zr(FeV)0.05 La2 O3 |
| 20% by |
| 198 240 less than 0.4 kg/cm2 |
| weight within 180 min. |
| 5 Zr(FeV)0.05 CeO2 |
| 20% by |
| 198 240 less than 0.4 kg/cm2 |
| weight within 180 min. |
| 6 Zr(FeV)0.05 mixed rare |
| 20% by |
| 194 240 less than 0.4 kg/cm2 |
| earth oxide weight within 180 min. |
| 7 Zr(FeV)0.1 La2 O3 |
| 20% by |
| 182 220 less than 0.4 kg/cm2 |
| weight within 180 min. |
| 8 Zr(FeV)0.1 CeO2 |
| 20% by |
| 180 220 less than 0.4 kg/cm2 |
| weight within 180 min. |
| 9 Zr(FeV)0.1 mixed rare |
| 20% by |
| 180 220 less than 0.4 kg/cm2 |
| earth oxide weight within 180 min. |
| 10 Zr(FeV)0.19 La2 O3 |
| 1% by |
| 170 200 less than 0.01 kg/cm2 |
| weight within 120 min. |
| 11 Zr(FeV)0.19 CeO2 |
| 1% by |
| 167 200 less than 0.01 kg/cm2 |
| weight within 120 min. |
| 12 Zr(FeV)0.19 mixed rare |
| 1% by |
| 168 200 less than 0.01 kg/cm2 |
| earth oxide weight within 120 min. |
| 13 Zr(FeV)0.19 La2 O3 |
| 5% by |
| 160 30 less than 0.01 kg/cm2 |
| weight within 15 min. |
| 14 Zr(FeV)0.19 CeO2 |
| 5% by |
| 160 30 less than 0.01 kg/cm2 |
| weight within 15 min. |
| 15 Zr(FeV)0.19 mixed rare |
| 5% by |
| 158 40 less than 0.01 kg/cm2 |
| earth oxide weight within 15 min. |
| 16 Zr(FeV)0.19 La2 O3 |
| 10% by |
| 156 room temp- |
| less than 0.01 kg/cm2 |
| weight erature (30) |
| within 10 min. |
| 17 Zr(FeV)0.19 CeO2 |
| 10% by |
| 154 room temp- |
| less than 0.01 kg/cm2 |
| weight erature (30) |
| within 10 min. |
| 18 Zr(FeV)0.19 Sm2 O3 |
| 10% by |
| 154 room temp- |
| less than 0.01 kg/cm2 |
| weight erature (30) |
| within 10 min. |
| 19 Zr(FeV)0.19 Eu2 O3 |
| 10% by |
| 153 room temp- |
| less than 0.01 kg/cm2 |
| weight erature (30) |
| within 10 min. |
| 20 Zr(FeV)0.19 mixed rare |
| 10% by |
| 151 room temp- |
| less than 0.01 kg/cm2 |
| earth oxide weight erature (30) |
| within 10 min. |
| 21 Zr(FeV)0.19 La2 O3 |
| 20% by |
| 145 room temp- |
| less than 0.01 kg/cm2 |
| weight erature (30) |
| within 10 min. |
| 22 Zr(FeV)0.19 CeO2 |
| 20% by |
| 142 room temp- |
| less than 0.01 kg/cm2 |
| weight erature (30) |
| within 5 min. |
| 23 Zr(FeV)0.19 Sm2 O3 |
| 20% by |
| 142 room temp- |
| less than 0.01 kg/cm2 |
| weight erature (30) |
| within 5 min. |
| 24 Zr(FeV)0.19 Eu2 O3 |
| 20% by |
| 143 room temp- |
| less than 0.01 kg/cm2 |
| weight erature (30) |
| within 5 min. |
| 25 Zr(FeV)0.19 mixed rare |
| 20% by |
| 140 room temp- |
| less than 0.01 kg/cm2 |
| earth oxide weight erature (30) |
| within 5 min. |
| 26 Zr(FeV)0.55 La2 O3 |
| 20% by |
| 125 room temp- |
| less than 0.01 kg/cm2 |
| weight erature (30) |
| within 4 min. |
| 27 Zr(FeV)0.55 CeO2 |
| 20% by |
| 123 room temp- |
| less than 0.01 kg/cm2 |
| weight erature (30) |
| within 4 min. |
| 28 Zr(FeV)0.55 mixed rare |
| 20% by |
| 122 room temp- |
| less than 0.01 kg/cm2 |
| earth oxide weight erature (30) |
| within 4 min. |
| 29 Zr(FeV)0.88 La2 O3 |
| 20% by |
| 110 room temp- |
| less than 0.01 kg/cm2 |
| weight erature (30) |
| within 4 min. |
| 30 Zr(FeV)0.88 CeO2 |
| 20% by |
| 107 room temp- |
| less than 0.01 kg/cm2 |
| weight erature (30) |
| within 2 min. |
| 31 Zr(FeV)0.88 mixed rare |
| 20% by |
| 105 room temp- |
| less than 0.01 kg/cm2 |
| earth oxide weight erature (30) |
| within 2 min. |
| __________________________________________________________________________ |
Saito, Takuya, Suzuki, Jo, Hirosawa, Kimihiko, Yamaguchi, Tamotu, Terazawa, Shotaro
| Patent | Priority | Assignee | Title |
| Patent | Priority | Assignee | Title |
| 4163666, | Jan 31 1978 | Hydrogen charged alloys of Zr(A1-x Bx)2 and method of hydrogen storage | |
| 4358429, | Oct 06 1981 | The United States of America as represented by the United States | Oxygen stabilized zirconium vanadium intermetallic compound |
| 4375257, | Jan 24 1969 | U.S. Philips Corporation | Hydrogen storage and supply device |
| 4555395, | Sep 27 1982 | Standard Oil Company | Hydride compositions |
| 4565686, | Jan 21 1981 | The Charles Stark Draper Laboratory, Inc. | Method of storing hydrogen using nonequilibrium materials and system |
| 4629720, | Dec 04 1984 | Suzuki Shokan Co., Ltd. | Substance for reversibly absorbing and desorbing hydrogen |
| 4661415, | Oct 27 1984 | Nihon Yakin Kogyo Kabushiki Kaisha | Hydrogen absorbing zirconium alloy |
| JP57102935, |
| Executed on | Assignor | Assignee | Conveyance | Frame | Reel | Doc |
| May 11 1987 | SUZUKI, JO | SUZUKI SHOKAN CO , LTD | ASSIGNMENT OF ASSIGNORS INTEREST | 004715 | /0871 | |
| May 11 1987 | HIROSAWA, KIMIHIKO | SUZUKI SHOKAN CO , LTD | ASSIGNMENT OF ASSIGNORS INTEREST | 004715 | /0871 | |
| May 11 1987 | YAMAGUCHI, TAMOTU | SUZUKI SHOKAN CO , LTD | ASSIGNMENT OF ASSIGNORS INTEREST | 004715 | /0871 | |
| May 11 1987 | SAITO, TAKUYA | SUZUKI SHOKAN CO , LTD | ASSIGNMENT OF ASSIGNORS INTEREST | 004715 | /0871 | |
| May 11 1987 | TERAZAWA, SHOTARO | SUZUKI SHOKAN CO , LTD | ASSIGNMENT OF ASSIGNORS INTEREST | 004715 | /0871 | |
| May 27 1987 | Suzuki Shokan Co., Ltd. | (assignment on the face of the patent) | / |
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